Upgrading of Bio-Oil by Reaction with Olefins in the Presence of a Catalyst

ABSTRACT

Systems, methods, and apparatuses are provided for upgrading a bio-oil by reaction with an olefin in the presence of a catalyst. For example, upgraded bio-oil may have improved miscibility with hydrophobic fuels.

This application claims priority from U.S. Provisional Patent Application Nos. 61/843,449, filed on Jul. 8, 2013, and 61/861,027, filed Aug. 1, 2013, each of which are entirely incorporated herein by reference.

BACKGROUND

The extraction of bio-oil from biomass for use as a biofuel is an area of interest in the search for reliable alternative energy sources. Biomass such as, for example, lignocellulosic substances (e.g., wood), may be subjected to pyrolysis to create a hot pyrolysis vapor. Bio-oil may be extracted from the hot pyrolysis vapor. Bio-oil from pyrolysis of wood may contain a mixture of water, organic acids, aldehydes, phenols, and sugar derivatives. Bio-oil from pyrolysis of wood may be characterized by undesirably or unacceptably high hydroxyl value, acid value, or water concentration. For example, mixtures may exhibit varying degrees of miscibility/immiscibility with other fuels, particularly in view of the combination of hydrophobic oil characteristics with hydrophilic species such as water, organic acids, etc. Consequently, high hydroxyl value, acid value, and water concentration may be detrimental, for example, to fuel value, fuel miscibility, and thermal stability.

The present application appreciates that extraction of bio-oil from biomass for use as a biofuel may be a challenging endeavor.

SUMMARY

In an embodiment, a method for upgrading a bio-oil is provided. The method may include contacting the bio-oil with an olefin in the presence of a catalyst. Compared to the bio-oil, the upgraded bio-oil may include one or more of: a reduced hydroxyl value; a reduced acid value; a reduced polarity; a reduced miscibility in a polar solvent; a reduced oxygen concentration, a reduced water concentration; or an increased average molecular weight.

In an embodiment, a method for upgrading a bio-oil in a vapor phase is provided. The method may include providing a vapor phase bio-oil. The method may also include contacting the vapor phase bio-oil with an olefin in the presence of a catalyst to provide an upgraded bio-oil.

In an embodiment, a process for converting pyrolysis oil to a hydrocarbon fuel is provided. The process may include reacting a pyrolysis oil in a reactor with a feed in the presence of a catalyst. The feed may include one or more olefin species. A product mixture may be formed including at least one of an esterification and an etherification product. The process may also include contacting the at least one of the esterification and the etherification product in a reaction zone with a hydrotreating catalyst in the presence of hydrogen. The process in the reaction zone may be conducted under reaction conditions sufficient to convert at least a portion of the at least one of the esterification and the etherification product into one or more fuel range hydrocarbon products.

In an embodiment, an upgraded bio-oil is provided. The upgraded bio-oil may be produced by a process including contacting a crude bio-oil with an olefin in the presence of a catalyst to form the upgraded bio-oil. The upgraded bio-oil may be characterized compared to the crude bio-oil by one or more of: a reduced hydroxyl value; a reduced acid value; a reduced polarity; a reduced miscibility in a polar solvent; a reduced oxygen concentration, a reduced water concentration; or an increased average molecular weight.

In an embodiment, a composition including one or more hydrocarbon fuel range products is provided. The mixture of one or more hydrocarbon fuel range products may be produced from a pyrolysis oil by a process. The process may include reacting the pyrolysis oil with a feed including an olefin in the presence of a catalyst. A product mixture may be formed including at least one of an esterification product and an etherification product. The process may also include contacting the at least one of the esterification product and the etherification product in a reaction zone with a hydrotreating catalyst in the presence of hydrogen. The process in the reaction zone may be conducted under reaction conditions sufficient to convert at least a portion of the at least one of the esterification product and the etherification product into the mixture of the one or more fuel range hydrocarbon products.

In an embodiment, a method of improving miscibility of a bio-oil in a hydrophobic fuel is provided. The method may include providing a miscible bio-oil. The miscible bio-oil may be upgraded, catalytic, or upgraded and catalytic compared to a starting material bio-oil. The method may also include contacting the miscible bio-oil to a hydrophobic fuel to form a miscible mixture. The miscible bio-oil may be characterized by greater miscibility in the hydrophobic fuel compared to the bio-oil starting material.

In various embodiments, a bio-oil composition is provided. The bio-oil composition may include a miscible ternary mixture. The miscible ternary mixture may be composed according to each triplet of miscible or partly miscible ranges in any one of FIG. 7A, 7B, 7C, or 7D, or a combination thereof. The miscible ternary mixture may include a bio-oil, an upgraded (modified) bio-oil, a catalytic bio-oil, or an upgraded and catalytic bio-oil in a percentage according to each corresponding range in FIG. 7A, 7B, 7C, or 7D. The miscible ternary mixture may include an alcohol in a percentage according to each corresponding range of 1-butanol in FIG. 7A, 7B, 7C, or 7D. The miscible ternary mixture may include a hydrophobic fuel in a percentage according to each corresponding range of diesel in FIG. 7A, 7B, 7C, or 7D.

BRIEF DESCRIPTION OF THE DRAWINGS

The accompanying FIGs., which are incorporated in and constitute a part of the specification, illustrate example methods, and are used merely to illustrate an example embodiment.

FIG. 1 is a chemical scheme showing that acidity may be reduced by esterification with an alcohol or an olefin;

FIG. 2 is a chemical scheme showing reduced hydroxyl value by acetalization of hydroxyls with aldehyde;

FIG. 3 is a chemical scheme showing reduced hydroxyl value by etherification of hydroxyls with olefin;

FIG. 4 is a flow diagram of a method for reducing at least one of a hydroxyl value, an acid value, and a water concentration in a bio-oil;

FIG. 5 is a flow diagram of a method for upgrading a bio-oil in a vapor phase;

FIG. 6 is a flow diagram of a process for converting a pyrolysis oil to one or more hydrocarbon fuel range products;

FIG. 7A is an example ternary phase diagram summarizing miscibility results versus proportions of diesel fuel, 1-butanol, and bio-oil of Example 5;

FIG. 7B is an example ternary phase diagram summarizing miscibility results versus proportions of diesel fuel, 1-butanol, and modified catalytic bio-oil of Example 6;

FIG. 7C is an example ternary phase diagram summarizing miscibility results versus proportions of diesel fuel, 1-butanol, and modified bio-oil of Example 7;

FIG. 7D is an example ternary phase diagram summarizing miscibility results versus proportions of diesel fuel, 1-butanol, and catalytic bio-oil;

FIG. 8 is a flow diagram of an example method of improving miscibility of a bio-oil in a hydrophobic fuel.

DETAILED DESCRIPTION

Bio-oil may be obtained from the pyrolysis of various woods. The resulting bio-oil may contain a mixture of organic acids, aldehydes, phenols, and sugar derivatives that may be detrimental to fuel value, fuel miscibility, and thermal stability. Producing bio-oil by pyrolysis may also produce significant amounts of water. These characteristics may be improved through the reaction of acids, phenols, and sugar with olefins to form other compounds such as alcohols, ethers, and esters.

Briefly described, in an aspect of the invention, a method of bio-oil upgrading may increase bio-oil solubility in fuels such as diesel and may reduce undesirable attributes of bio-oil. The method may include reacting the bio-oil with olefins in the presence of a catalyst. The method may independently or collectively remove water, etherify hydroxyls, and/or esterify carboxylic acids.

Briefly described, in another aspect of the present invention, a method for upgrading bio-oil may include passing vapor phase bio-oil through a catalyst bed after mixing with an injected amount of olefin and reacting to upgrade the vapor phase bio-oil. For example, at least a portion of hydroxyls in the vapor phase bio-oil may become ethers. In another example, at least a portion of carboxylic acids in the vapor phase bio-oil may become esters. In a further example, at least a portion of water present in the vapor phase bio-oil may be converted to an alcohol form of the olefin. Benefits of the method for upgrading vapor phase bio-oil may include lower equipment costs and/or faster reactions due to increased temperatures. Although water may be undesirable at high amounts, alcohol produced by reacting the water with the olefin at the catalyst may be purified to provide a higher value material.

FIG. 1 is a chemical scheme showing that acidity may be reduced by esterification with an alcohol or an olefin. A common problem with bio-oil may be acidity from carboxylic acids such as acetic acid. Esterification, as shown in FIG. 1, may remove the acidity and may also maintain bio-oil mass. Esterification of a carboxylic acid with an alcohol may include the use of heat over extended time in order to remove water and shift the reaction equilibrium toward the ester. Furthermore, bio-oil may contain various sugars, and heating under acidic conditions may cause caramelization to occur. Esterification by reaction of carboxylic acids with an olefin according to the described method may be favorable, for example, because energetically costly water removal may be omitted and caramelization may be avoided or reduced.

FIG. 2 is a chemical scheme showing reduced hydroxyl value by acetalization of hydroxyls with aldehyde. Hydroxyls originating from the breakdown of cellulose into sugars may be problematic in bio-oil. The process depicted in FIG. 2 shows the reaction of 1,2-diols or 1,3-diols with an aldehyde to form an acetal plus water. The reaction of FIG. 2 may be favored by removing water from the reaction mixture. However, the reaction of FIG. 2 may not remove any acidity and may also be associated with energetically costly water removal.

FIG. 3 depicts reduced hydroxyl value by etherification of hydroxyls with olefin The reaction of FIG. 3 may be water independent and may therefore be favorable compared to the reaction of FIG. 2. One reaction not specified above involves the acid catalyzed reaction of olefins with water to initially form alcohols that may react further with water to form dialkyl ethers. This reaction removes water from the bio-oil reaction mixtures that advantageously results in reduced hydrolysis of esters back to carboxylic acids. Another reaction not specified above is the acid-catalyzed addition of water to olefins to form alcohols, thus reducing the bio-oil content and reducing ester and acetal hydrolysis. For example, 2-propanol is produced by the reaction of propylene with water over a resin acid catalyst. This may make the olefin reaction more favorable as it may react with various non-desired attributes of bio-oil, e.g., free hydroxyls, carboxyls, water, and the like.

FIG. 4 is a flow diagram of a method 400 for upgrading a bio-oil. The method 400 may include 402 contacting the bio-oil with an olefin in the presence of a catalyst to 404 form the upgraded bio-oil. Compared to the bio-oil, the upgraded bio-oil may include one or more of: a reduced hydroxyl value; a reduced acid value; a reduced polarity; a reduced miscibility in a polar solvent; a reduced oxygen concentration, a reduced water concentration; or an increased average molecular weight. The catalyst may cause a reaction between the olefin and one or more components of the bio-oil, such as a hydroxyl group, a carboxylic acid group, and the water. The reaction may be a vapor phase catalytic reaction.

As used herein, the catalyst may be a solid, liquid, or vapor composition that catalyzes the reaction between the bio-oil and the olefin. For example, the catalyst may include one or more of a solid catalyst such as a solid acid catalyst, a transition metal catalyst including metal oxides and organometallic complexes, and the like. The catalyst may be in liquid or vapor form, such as liquid or vapor HCl or H₂SO₄. In some embodiments, the catalyst may include a solid resin acid catalyst, such as supported propylsulfonic acid.

In some embodiments of the method for reducing at least one of a hydroxyl value, an acid value, and a water concentration in a bio-oil, the method may include pyrolyzing a biomass to form the bio-oil. The pyrolyzing the biomass to form the bio-oil may be conducted prior to contacting the bio-oil with the olefin in the presence of the catalyst.

In several embodiments of the method for reducing at least one of a hydroxyl value, an acid value, and a water concentration in a bio-oil, the olefin may include a C₃-C₅ alkene. As used herein, a C₃-C₅ alkene may include a linear, branched or cyclic alkylene compound that includes at least one carbon-carbon double bond, e.g., propylene, 2-methylpropene (isobutylene), 1-butene, 2-butene, 1,3 butadiene, 2-methyl-1,3 butadiene (isoprene), cyclopropene, cyclobutene, cyclopentene, cyclopentadiene, or the like. For example, the olefin may include at least one of propylene, isobutylene, and isoprene.

In various embodiments of the method for reducing at least one of a hydroxyl value, an acid value, and a water concentration in a bio-oil, the method may include contacting the bio-oil with a hydrogen donor, e.g., the hydrogen donor described herein.

In various embodiments, the olefin may be fed alone to the reaction. The olefin may also be fed to the reaction in combination with the hydrogen donor. The olefin and hydrogen donor may be independently fed to the reaction. The olefin and/or hydrogen donor may be fed to the reaction in any stage, for example: in combination with biomass, during pyrolysis of biomass to provide the bio-oil, directly to the reaction at the catalyst, after reaction at the catalyst, after bio-oil condensation, and the like.

In several embodiments of the method for reducing at least one of a hydroxyl value, an acid value, and a water concentration in a bio-oil, the bio-oil may be at least partially in a vapor phase. In some embodiments, the bio-oil may be substantially or completely in the vapor phase. The bio-oil may contain water. The water may be, independently or together with the bio-oil, at least partially, substantially, or completely in the vapor phase.

FIG. 5 is a flow diagram of a method 500 for upgrading a bio-oil in a vapor phase. The method 500 may include 502 providing a vapor phase bio-oil. The method 500 may also include 504 contacting the vapor phase bio-oil with an olefin in the presence of a catalyst to provide an upgraded bio-oil. The catalyst may cause a reaction between the olefin and one or more components of the bio-oil, such as a hydroxyl group, a carboxylic acid group, and the water. The reaction may be a vapor phase catalytic reaction.

In various embodiments, the method for upgrading a bio-oil in a vapor phase may include mixing the vapor phase bio-oil with the olefin in gas or vapor form to provide a vapor phase mixture of bio-oil and olefin. The method may also include contacting the vapor phase mixture of bio-oil and olefin to the catalyst to provide the upgraded bio-oil.

In some embodiments, the method for upgrading a bio-oil in a vapor phase may be conducted as a continuous process or a batch process.

In several embodiments, the method for upgrading a bio-oil in a vapor phase, providing the vapor phase bio-oil may include pyrolyzing a biomass to form the vapor phase bio-oil.

In various embodiments, the olefin may include a C₃-C₅ alkene as described herein.

In various embodiments of the method for upgrading a bio-oil in a vapor phase, the method may include contacting the bio-oil with a hydrogen donor. As used herein, the hydrogen donor may include a C₁-C₁₀ aliphatic compound that includes at least one hydroxyl group bonded to an alkyl carbon. For example, the hydrogen donor may include a C₁-C₁₀ linear, branched, or cyclic aliphatic compound that includes a hydroxyl group bonded to an alkyl carbon, such as an alcohol, a polyol such as a diol, and the like. For example, the method may include contacting the bio-oil with a C₃-C₅ alcohol. The C₃-C₅ alcohol may include, for example, 1-propanol, 2-propanol, 1-butanol, 2-butanol, sec-butyl alcohol, tert-butyl alcohol, 1-pentanol, 2-pentanol, cyclopropanol, cyclobutanol, cyclopentanol, or the like. The hydrogen donor may also include diols such as ethylene glycol, propylene glycol, and the like. The hydrogen donor may also include higher polyols such as triols including glycerol, and the like. In some embodiments, the hydrogen donor may include at least one of a C₃-C₅ alcohol, a C₃-C₅ diol, or a C₃-C₅ triol.

In various embodiments, the olefin may be fed alone to the reaction. The olefin may also be fed to the reaction in combination with the hydrogen donor. The olefin and hydrogen donor may be independently fed to the reaction. The olefin and/or hydrogen donor may be fed to the reaction in any stage, for example: in combination with biomass, during pyrolysis of biomass to provide the bio-oil, directly to the reaction at the catalyst, after reaction at the catalyst, after upgraded bio-oil condensation, and the like.

In some embodiments, the method for upgrading a bio-oil in a vapor phase using a catalyst may include any catalyst described herein. For example, the method for upgrading a bio-oil in a vapor phase may include using a supported propylsulfonic acid.

In several embodiments, the method for upgrading a bio-oil in a vapor phase, the vapor phase bio-oil may include water. The method may also include separating an alcohol from the upgraded bio-oil. The alcohol may be produced by contacting the vapor phase bio-oil including water with the olefin in the presence of the catalyst.

In various embodiments, an upgraded bio-oil is provided. In some embodiments, the upgraded bio-oil may be produced by a process including contacting a crude bio-oil with an olefin in the presence of a catalyst to form the upgraded bio-oil. The upgraded bio-oil may be characterized compared to the crude bio-oil by one or more of: a lower hydroxyl value; a lower acid value; lower polarity; lower miscibility in a polar solvent, such as water; lower oxygen concentration, e.g, measured via elemental analysis; different molecular weight or molecular weight distribution, e.g., higher molecular weight; or a lower water concentration. In several embodiments, the upgraded bio-oil may be produced by a process including providing a vapor phase bio-oil. The process may also include contacting the vapor phase bio-oil with an olefin in the presence of a catalyst to provide an upgraded bio-oil. In various embodiments, the process for producing the upgraded bio-oil may include any subject matter described for the various methods herein.

FIG. 6 is a flow diagram of a process 600 for converting a pyrolysis oil to one or more hydrocarbon fuel range products. The process may include 602 reacting a pyrolysis oil with a feed including an olefin in the presence of a catalyst. The process may 604 form a product mixture including at least one of an esterification product and an etherification product. The process may also include 606 contacting the at least one of the esterification product and the etherification product in a reaction zone with a hydrotreating catalyst in the presence of hydrogen. The process may be conducted in the reaction zone under reaction conditions sufficient to convert at least a portion of the at least one of the esterification product and the etherification product into one or more fuel range hydrocarbon products.

In some embodiments, the process for converting the pyrolysis oil to one or more hydrocarbon fuel range products may include pyrolyzing a biomass to form the pyrolysis oil. The pyrolyzing the biomass to form the pyrolysis oil may be conducted prior to reacting the pyrolysis oil with the feed including the olefin in the presence of the catalyst.

In several embodiments of the process for converting the pyrolysis oil to one or more hydrocarbon fuel range products, the olefin may include a C₃-C₅ alkene as described herein. For example, the olefin may include at least one of propylene, isobutylene, and isoprene.

In various embodiments, the process for converting the pyrolysis oil to one or more hydrocarbon fuel range products may include contacting the pyrolysis oil with a hydrogen donor, e.g., the hydrogen donor described herein.

In various embodiments, the olefin may be fed alone to process 600. The olefin may also be fed to process 600 in combination with the hydrogen donor. The olefin and hydrogen donor may be independently fed to process 600. The olefin and/or hydrogen donor may be fed to process 600 in any stage of process 600. For example, the olefin and/or hydrogen donor may be fed to the reaction: in combination with biomass to be pyrolyzed, during pyrolysis of biomass to provide the pyrolysis oil, directly to the reaction at the catalyst, after reaction at the catalyst, after pyrolysis oil condensation, and the like.

In several embodiments of the process for converting the pyrolysis oil to one or more hydrocarbon fuel range products, the catalyst may include any catalyst described herein, for example, a solid acid catalyst such as a supported alkylsulfonic acid. For example, the supported sulfonic acid may include supported propylsulfonic acid.

In several embodiments of the process for converting the pyrolysis oil to one or more hydrocarbon fuel range products, the pyrolysis oil may be at least partially in a vapor phase.

In several embodiments of the process for converting the pyrolysis oil to one or more hydrocarbon fuel range products, the hydrotreating catalyst may include one or more catalysts, or a combination or composite thereof. Suitable hydrotreating catalysts may include cobalt (Co), molybdenum (Mo), nickel (Ni), titanium (Ti), tungsten (W), zinc (Zn), antimony (Sb), bismuth (Bi), cerium (Ce), vanadium (V), niobium (Nb), tantalum (Ta), chromium (Cr), manganese (Mn), rhenium (Re), iron (Fe), platinum (Pt), iridium (Ir), palladium (Pd), osmium (Os), rhodium (Rh), ruthenium (Ru), nickel, copper impregnated zinc oxide (Cu/ZnO), copper impregnated chromium oxide (Cu/Cr), nickel aluminum oxide (Ni/Al₂O₃), palladium aluminum oxide (PdAl₂O₃), cobalt molybdenum (CoMo), nickel molybdenum (NiMo), nickel molybdenum tungsten (NiMoW), sulfided cobalt molybdenum (CoMo), sulfided nickel molybdenum (NiMo), a metal carbide, or a composite or combination thereof. The hydrotreating catalyst may include a metal oxide support. Suitable metal oxide supports may include one or more of a titanium oxide (TiO₂) support, a silicon oxide support, a zirconia oxide (ZrO₂) support, a niobium oxide (Nb₂O₅) support, a support including one or more mixtures of non-alumina metal oxides, or a combination or composite thereof. The hydrotreating catalyst may also include a noble metal composition on the metal oxide support. Suitable noble metals for the noble metal composition may include one or more of rhodium (Rh), palladium (Pd), gold (Au), ruthenium (Ru), or a combination or composite thereof.

In various embodiments, a composition including one or more hydrocarbon fuel range products is provided. The mixture of one or more hydrocarbon fuel range products may be produced from a pyrolysis oil by a process, such as process 600. The process may include reacting the pyrolysis oil with a feed including an olefin in the presence of a catalyst. The process may form a product mixture including at least one of an esterification product and an etherification product. The process may include contacting the at least one of the esterification product and the etherification product in a reaction zone with a hydrotreating catalyst in the presence of hydrogen. The process in the reaction zone may be conducted under reaction conditions sufficient to convert at least a portion of the at least one of the esterification product and the etherification product into the mixture of the one or more fuel range hydrocarbon products.

The process for producing the mixture of one or more hydrocarbon fuel range products may include any subject matter described herein for the process for converting the pyrolysis oil to one or more hydrocarbon fuel range products.

Bio-oil starting material may be produced from pyrolysis of biomass. Catalytic bio-oil starting material may be produced from pyrolysis of biomass using a catalyst. These bio-oil starting materials contain a mixture of water, organic acids, aldehydes, phenols, free hydroxyls, and sugar derivatives which may impact miscibility and fuel quality, particularly with hydrophobic fuels such as diesel.

Briefly stated, the present invention includes methods and compositions relating to improved bio-oil miscibility in hydrophobic fuel. For example, the method may include providing a miscible bio-oil. The miscible bio-oil may be upgraded, catalytic, or upgraded and catalytic compared to a starting material bio-oil. The method may also include contacting the upgraded bio-oil to a hydrophobic fuel to form a miscible mixture. The upgraded bio-oil may be characterized by greater miscibility in the hydrophobic fuel compared to the bio-oil starting material

For example, FIG. 7A depicts an example ternary phase diagram illustrating the miscibility relationships between bio-oil, diesel, and 1-butanol. FIG. 7B depicts an example ternary phase diagram illustrating the miscibility relationships between modified catalytic bio-oil, diesel, and 1-butanol. FIG. 7C depicts an example ternary phase diagram illustrating the miscibility relationships between modified bio-oil, diesel, and 1-butanol. FIG. 7D depicts an example ternary phase diagram illustrating the miscibility relationships between catalytic bio-oil, diesel, and 1-butanol. As can be seen in FIG. 7A, 7B, 7C, or 7D, higher amounts of alcohol and lower amounts of diesel may be employed with bio-oil starting material that is neither upgraded nor produced using a catalytic pyrolysis of biomass. However, catalytic bio-oil may improve miscibility with diesel compared to bio-oil prepared by pyrolysis without catalysis. Upgrading (modification) of the bio-oils (both catalytic and non-catalytic) may miscibility, in some examples, significantly. The phase diagrams also show that it may be easier to dissolve low amounts of diesel into high amounts of bio-oil compared to low amounts of bio-oil into high amounts of diesel. This may be due to the polar nature of bio-oil versus the non-polarity of diesel fuel.

FIG. 8 depicts an example method 800 of improving miscibility of a bio-oil in a hydrophobic fuel. The method 800 may include 802 providing a miscible bio-oil. The miscible bio-oil may be upgraded, catalytic, or upgraded and catalytic compared to a starting material bio-oil. The method may also include 804 contacting the miscible bio-oil to a hydrophobic fuel to form a miscible mixture. The miscible bio-oil may be characterized by greater miscibility in the hydrophobic fuel compared to the bio-oil starting material.

In some embodiments, the method may also include contacting an alcohol to the miscible bio-oil and the hydrophobic fuel to form the miscible mixture. The alcohol may include a C₃-C₅ alcohol. The alcohol may include one or more of n-butanol, sec-butanol, iso-butanol, tert-butanol, n-propanol, or 2-propanol.

In several embodiments, the method may also include contacting a surfactant to the miscible bio-oil and the hydrophobic fuel to form the miscible mixture. The surfactant may include one or more of an anionic surfactant, a cationic surfactant, an amphiphilic surfactant, or a nonionic surfactant.

In various embodiments, the method may also include contacting a surfactant and an alcohol to the miscible bio-oil and the hydrophobic fuel to form the miscible mixture.

In some embodiments, the method may also include upgrading the bio-oil starting material to provide the miscible bio-oil by contacting the bio-oil starting material with an olefin in the presence of a solid acid catalyst to provide the miscible bio-oil. Additionally or alternatively, the method may also include upgrading the bio-oil starting material to provide the miscible bio-oil by contacting the bio-oil starting material with the olefin in a vapor phase in the presence of a catalyst to provide the miscible bio-oil. The miscible bio-oil may be reduced in one or more of a hydroxyl value, an acid value, or a water concentration compared to the bio-oil starting material.

Various embodiments include a method for reducing at least one of a hydroxyl value, an acid value, and a water concentration in a bio-oil, for example, to provide the miscible bio-oil as upgraded bio-oil. The method may include contacting the bio-oil starting material with an olefin in the presence of a solid acid catalyst to reduce at least one of the hydroxyl value, the acid value, and the water concentration.

In some embodiments of the method for reducing at least one of a hydroxyl value, an acid value, and a water concentration in a bio-oil, the method may include pyrolyzing a biomass to form the bio-oil. The pyrolyzing the biomass to form the bio-oil may be conducted prior to contacting the bio-oil with the olefin in the presence of the solid acid catalyst.

In several embodiments of the method for reducing at least one of a hydroxyl value, an acid value, and a water concentration in a bio-oil, the olefin may include a C₃-C₅ alkene as described herein.

In various embodiments of the method for reducing at least one of a hydroxyl value, an acid value, and a water concentration in a bio-oil, the method may include contacting the bio-oil with an alcohol. As used herein, an alcohol may include a C₁-C₁₀ linear, branched, or cyclic aliphatic compound that includes a hydroxyl group bonded to an alkyl carbon. For example, the method may include contacting the bio-oil with a C₃-C₅ alcohol. The C₃-C₅ alcohol may include, for example, 1-propanol, 2-propanol, 1-butanol, 2-butanol, sec-butyl alcohol, tert-butyl alcohol, 1-pentanol, 2-pentanol, cyclopropanol, cyclobutanol, cyclopentanol, or the like.

In some embodiments of the method for reducing at least one of a hydroxyl value, an acid value, and a water concentration in a bio-oil, the solid acid catalyst may include a supported propylsulfonic acid.

In several embodiments of the method for reducing at least one of a hydroxyl value, an acid value, and a water concentration in a bio-oil, the bio-oil may be at least partially in a vapor phase. In some embodiments, the bio-oil may be substantially or completely in the vapor phase. The bio-oil may contain water. The water may be, independently or together with the bio-oil, at least partially, substantially, or completely in the vapor phase.

Various embodiments include a method for upgrading a bio-oil in a vapor phase. The method may include providing a vapor phase bio-oil starting material. The method may also include contacting the vapor phase bio-oil starting material with an olefin in the presence of a catalyst to provide an upgraded bio-oil.

In various embodiments, the method for upgrading a bio-oil in a vapor phase may include mixing the vapor phase bio-oil with the olefin in gas or vapor form to provide a vapor phase mixture of bio-oil and olefin. The method may also include contacting the vapor phase mixture of bio-oil and olefin to the catalyst to provide the upgraded bio-oil.

In some embodiments, the method for upgrading a bio-oil in a vapor phase may be conducted as a continuous process or a batch process.

In several embodiments, the method for upgrading a bio-oil in a vapor phase may the providing the vapor phase bio-oil including pyrolyzing a biomass to form the vapor phase bio-oil.

In various embodiments, the method for upgrading a bio-oil in a vapor phase the olefin including a C₃-C₅ alkene. The olefin may include one or more of propylene, isobutylene, or isoprene.

In some embodiments, the method for upgrading a bio-oil in a vapor phase solid acid catalyst including a supported propylsulfonic acid.

In several embodiments, the method for upgrading a bio-oil in a vapor phase, the vapor phase bio alcohol may include water. The method may also include separating an alcohol from the upgraded bio-oil. The alcohol may be produced by contacting the vapor phase bio-oil including water with the olefin in the presence of the catalyst.

In various embodiments, an upgraded bio-oil is provided. In some embodiments, the upgraded bio-oil may be produced by a process including contacting a crude bio-oil with an olefin in the presence of a solid acid catalyst to form the upgraded bio-oil. The upgraded bio-oil may be characterized compared to the crude bio-oil by one or more of a lower hydroxyl value, a lower acid value, or a lower water concentration. In several embodiments, the upgraded bio-oil may be produced by a process including providing a vapor phase bio-oil. The process may also include contacting the vapor phase bio-oil with an olefin in the presence of a catalyst to provide an upgraded bio-oil. In various embodiments, the process for producing the upgraded bio-oil may include any subject matter described for the various methods herein.

In several embodiments of the method of improving miscibility of a bio-oil in a hydrophobic fuel, the hydrophobic fuel may include one or more of: diesel, fuel oil, heating oil, bunker fuel, gasoline, jet fuel, kerosene, white gas, liquefied coal fuel, or naphtha. For example, the hydrophobic fuel may be diesel.

In various embodiments of the method of improving miscibility of a bio-oil in a hydrophobic fuel, the bio-oil starting material including one or more of: water, organic acids, aldehydes, alkyl hydroxyls, phenols, or sugars.

In some embodiments, a bio-oil composition is provided. The bio-oil composition may include a miscible ternary mixture. The miscible ternary mixture may be composed according to each triplet of miscible or partly miscible ranges in any one of FIG. 7A, 7B, 7C, or 7D, or a combination thereof. The miscible ternary mixture may include a bio-oil, an upgraded (modified) bio-oil, a catalytic bio-oil, or an upgraded (modified) and catalytic bio-oil in a percentage according to each corresponding range in FIG. 7A, 7B, 7C, or 7D. The miscible ternary mixture may include an alcohol in a percentage according to each corresponding range of 1-butanol in FIG. 7A, 7B, 7C, or 7D. The miscible ternary mixture may include a hydrophobic fuel in a percentage according to each corresponding range of diesel in FIG. 7A, 7B, 7C, or 7D.

In several embodiments of the bio-oil composition, the miscible ternary mixture may be according to each triplet of miscible or partly miscible ranges in any one of FIG. 7B, 7C, or 7D, or a combination thereof. At least one said percentage may be within the corresponding miscible percentage range. Each said corresponding percentage range may be within each corresponding miscible percentage range.

In various embodiments of the bio-oil composition, the bio-oil composition may consist substantially of the miscible ternary mixture. The bio-oil composition may consist essentially of the miscible ternary mixture.

In some embodiments of the bio-oil composition, the alcohol may include a C₃-C₅ alcohol. For example, the alcohol may include one or more of n-butanol, sec-butanol, iso-butanol, tert-butanol, n-propanol, or 2-propanol.

In several embodiments of the bio-oil composition, the hydrophobic fuel may include one or more of: diesel, fuel oil, heating oil, bunker fuel, gasoline, jet fuel, kerosene, white gas, liquefied coal fuel, or naphtha. For example, the hydrophobic fuel may be diesel fuel.

In various embodiments of the bio-oil composition, the bio-oil composition may further include a surfactant. The surfactant may include one or more of an anionic surfactant, a cationic surfactant, an amphiphilic surfactant, or a nonionic surfactant

In some embodiments of the bio-oil composition, the miscible bio-oil may be prepared from a bio-oil starting material in a process including contacting the bio-oil starting material with an olefin in the presence of a solid acid catalyst to provide the miscible bio-oil. Additionally or alternatively, the process may include contacting the bio-oil starting material with the olefin in a vapor phase in the presence of a catalyst to provide the miscible bio-oil. The miscible bio-oil may be reduced in at least one of a hydroxyl value, an acid value, and a water concentration compared to the bio-oil starting material. The process for preparing the miscible bio-oil from a bio-oil starting material may include any subject matter described herein for preparing the miscible bio-oil.

EXAMPLES Example 1

A sample of bio-oil was obtained, and characterized for initial values of hydroxyl value, acid value, and approximate water concentration. A total value of moles of hydroxyl groups may be determined from the initial values of hydroxyl value, acid value, and approximate water concentration. The bio-oil was added to a stirring autoclave reactor. A few mole percent of a solid acid catalyst, propylsulfonic acid (SILIABOND®, SiliCycle Inc., Quebec, Canada), was added to the reactor. The mole percent may be determined versus the total value of moles of hydroxyl groups, for example, between about 0.1 mol % and about 10 mol %. The reactor was closed and purged. An amount of an olefin, propylene, was added as a gas. The amount of the olefin may be determined according to the total value of moles of hydroxyl groups, e.g., between about 0.1 mole equivalents and about 2 mole equivalents. The reactor was sealed. Multiple runs were performed with at different temperatures, at ambient temperature, at 90° C., and at 120° C. In some runs, alcohols such as 1-butanol or 1-propanol were used to homogenize the bio-oil and increase olefin solubility. Each run was stirred and allowed to react for 17 hours, and then poured into a jar, using simple filtration to remove the solid acid catalyst. The resulting upgraded bio-oil was then analyzed to determine hydroxyl value, acid value, and approximate water concentration. All three values were reduced significantly compared to the starting bio-oil.

Example 2

A sample of bio-oil was obtained, and characterized for initial values of hydroxyl value, acid value, and approximate water concentration. A total value of moles of hydroxyl groups may be determined from the initial values of hydroxyl value, acid value, and approximate water concentration. The bio-oil was added to a stirring autoclave reactor. A few mole percent of a solid acid catalyst, propylsulfonic acid (SILIABOND®, SiliCycle Inc., Quebec, Canada), was added to the reactor. The mole percent may be determined versus the total value of moles of hydroxyl groups, for example, between about 0.1 mol % and about 10 mol %. The reactor was closed and purged. An amount of an olefin, isobutylene, was added as a gas. The amount of the olefin may be determined according to the total value of moles of hydroxyl groups, e.g., between about 0.1 mole equivalents and about 2 mole equivalents. The reactor was sealed. Multiple runs were performed with at different temperatures, at ambient temperature, at 90° C., and at 120° C. In some runs, alcohols such as 1-butanol or 1-propanol were used to homogenize the bio-oil and increase olefin solubility. Each run was stirred and allowed to react for 17 hours, and then poured into a jar, using simple filtration to remove the solid acid catalyst. The resulting upgraded bio-oil was then analyzed to determine hydroxyl value, acid value, and approximate water concentration. All three values were reduced significantly compared to the starting bio-oil.

Example 3

A sample of bio-oil was obtained, and characterized for initial values of hydroxyl value, acid value, and approximate water concentration. A total value of moles of hydroxyl groups may be determined from the initial values of hydroxyl value, acid value, and approximate water concentration. The bio-oil was added to a stirring autoclave reactor. A few mole percent of a solid acid catalyst, propylsulfonic acid (SILIABOND®, SiliCycle Inc., Quebec, Canada), was added to the reactor. The mole percent may be determined versus the total value of moles of hydroxyl groups, for example, between about 0.1 mol % and about 10 mol %. The reactor was closed and purged. An amount of an olefin, isoprene, was added as a liquid. The amount of the olefin may be determined according to the total value of moles of hydroxyl groups, e.g., between about 0.1 mole equivalents and about 2 mole equivalents. The reactor was sealed, and the autoclave was pressurized with argon to about 90 pounds per square inch. Multiple runs were performed with at different temperatures, at ambient temperature, at 90° C., and at 120° C. In some runs, alcohols such as 1-butanol or 1-propanol were used to homogenize the bio-oil and increase olefin solubility. Each run was stirred and allowed to react for 17 hours, and then poured into a jar, using simple filtration to remove the solid acid catalyst. The resulting upgraded bio-oil was then analyzed to determine hydroxyl value, acid value, and approximate water concentration. All three values were reduced significantly compared to the starting bio-oil.

Example 4

A reactor was charged with a reaction mixture including about 58% w/w crude bio-oil, about 11% w/w 1-butanol, about 31% w/w isoprene, and about 0.15% (w/w compared to the crude bio-oil) of a solid acid catalyst, propylsulfonic acid (SILIABOND®, SiliCycle Inc., Quebec, Canada). The reactor was heated to 80° C. and pressurized to 90 pounds per square inch gauge, and stirred for 17 h to provide an upgraded bio-oil.

Example 5

Various proportions of crude bio-oil, diesel fuel, and 1-butanol were mixed and miscibility was determined FIG. 7A shows a phase diagram 700A summarizing the miscibility results versus the proportions of crude bio-oil, diesel fuel, and 1-butanol. FIG. 7A shows that more than 30% w/w of 1-butanol is required to emulsify the sample of crude bio-oil of EXAMPLE 5 in diesel fuel.

Example 6

A sample of upgraded catalytic bio-oil was obtained, prepared by catalytic pyrolysis of biomass followed by upgrading in a process similar to EXAMPLE 4. Various proportions of the upgraded catalytic bio-oil, diesel fuel, and 1-butanol were mixed and miscibility was determined FIG. 7B shows a phase diagram 700B summarizing the miscibility results versus the proportions of the upgraded catalytic bio-oil, diesel fuel, and 1-butanol. FIG. 7B shows that the sample of upgraded catalytic bio-oil of EXAMPLE 6 may be emulsified in diesel fuel with only about 20% w/w 1-butanol.

Example 7

A sample of upgraded bio-oil was obtained, prepared by pyrolysis of biomass followed by upgrading in a process similar to EXAMPLE 4. Various proportions of upgraded catalytic bio-oil, diesel fuel, and 1-butanol were mixed and miscibility was determined FIG. 7C is a phase diagram summarizing the miscibility results versus the proportions of upgraded bio-oil, diesel fuel, and 1-butanol. FIG. 7C shows a phase diagram 700C indicating that compared to the crude bio-oil of FIG. 7A, the sample of upgraded bio-oil of EXAMPLE 7 is significantly more miscible in diesel fuel.

To the extent that the term “includes” or “including” is used in the specification or the claims, it is intended to be inclusive in a manner similar to the term “comprising” as that term is interpreted when employed as a transitional word in a claim. Furthermore, to the extent that the term “or” is employed (e.g., A or B) it is intended to mean “A or B or both.” When the applicants intend to indicate “only A or B but not both” then the term “only A or B but not both” will be employed. Thus, use of the term “or” herein is the inclusive, and not the exclusive use. See Bryan A. Garner, A Dictionary of Modern Legal Usage 624 (2d. Ed. 1995). Also, to the extent that the terms “in” or “into” are used in the specification or the claims, it is intended to additionally mean “on” or “onto.” To the extent that the term “selectively” is used in the specification or the claims, it is intended to refer to a condition of a component wherein a user of the apparatus may activate or deactivate the feature or function of the component as is necessary or desired in use of the apparatus. To the extent that the term “operatively connected” is used in the specification or the claims, it is intended to mean that the identified components are connected in a way to perform a designated function. To the extent that the term “substantially” is used in the specification or the claims, it is intended to mean that the identified components have the relation or qualities indicated with degree of error as would be acceptable in the subject industry.

As used in the specification and the claims, the singular forms “a,” “an,” and “the” include the plural unless the singular is expressly specified. For example, reference to “a compound” may include a mixture of two or more compounds, as well as a single compounds.

As used herein, the term “about” in conjunction with a number is intended to include ±10% of the number. In other words, “about 10” may mean from 9 to 11.

As used herein, the terms “optional” and “optionally” mean that the subsequently described circumstance may or may not occur, so that the description includes instances where the circumstance occurs and instances where it does not.

In addition, where features or aspects of the disclosure are described in terms of Markush groups, those skilled in the art will recognize that the disclosure is also thereby described in terms of any individual member or subgroup of members of the Markush group. As will be understood by one skilled in the art, for any and all purposes, such as in terms of providing a written description, all ranges disclosed herein also encompass any and all possible sub-ranges and combinations of sub-ranges thereof. Any listed range can be easily recognized as sufficiently describing and enabling the same range being broken down into at least equal halves, thirds, quarters, fifths, tenths, etc. As a non-limiting example, each range discussed herein can be readily broken down into a lower third, middle third and upper third, etc. As will also be understood by one skilled in the art all language such as “up to,” “at least,” “greater than,” “less than,” include the number recited and refer to ranges which can be subsequently broken down into sub-ranges as discussed above. Finally, as will be understood by one skilled in the art, a range includes each individual member. For example, a group having 1-3 cells refers to groups having 1, 2, or 3 cells. Similarly, a group having 1-5 cells refers to groups having 1, 2, 3, 4, or 5 cells, and so forth. While various aspects and embodiments have been disclosed herein, other aspects and embodiments will be apparent to those skilled in the art.

As stated above, while the present application has been illustrated by the description of embodiments thereof, and while the embodiments have been described in considerable detail, it is not the intention of the applicants to restrict or in any way limit the scope of the appended claims to such detail. Additional advantages and modifications will readily appear to those skilled in the art, having the benefit of the present application. Therefore, the application, in its broader aspects, is not limited to the specific details, illustrative examples shown, or any apparatus referred to. Departures may be made from such details, examples, and apparatuses without departing from the spirit or scope of the general inventive concept.

As used herein, “substituted” refers to an organic group as defined below (e.g., an alkyl group) in which one or more bonds to a hydrogen atom contained therein may be replaced by a bond to non-hydrogen or non-carbon atoms. Substituted groups also include groups in which one or more bonds to a carbon(s) or hydrogen(s) atom may be replaced by one or more bonds, including double or triple bonds, to a heteroatom. A substituted group may be substituted with one or more substituents, unless otherwise specified. In some embodiments, a substituted group may be substituted with 1, 2, 3, 4, 5, or 6 substituents. Examples of substituent groups include: halogens (i.e., F, Cl, Br, and I); hydroxyls; alkoxy, alkenoxy, aryloxy, aralkyloxy, heterocyclyloxy, and heterocyclylalkoxy groups; carbonyls (oxo); carboxyls; esters; urethanes; oximes; hydroxylamines; alkoxyamines; aralkoxyamines; thiols; sulfides; sulfoxides; sulfones; sulfonyls; sulfonamides; amines; N-oxides; hydrazines; hydrazides; hydrazones; azides; amides; ureas; amidines; guanidines; enamines; imides; isocyanates; isothiocyanates; cyanates; thiocyanates; imines; nitro groups; or nitriles (i.e., CN). A “per”-substituted compound or group is a compound or group having all or substantially all substitutable positions substituted with the indicated substituent. For example, 1,6-diiodo perfluoro hexane indicates a compound of formula C₆F₁₂I₂, where all the substitutable hydrogens have been replaced with fluorine atoms.

Substituted ring groups such as substituted cycloalkyl, aryl, heterocyclyl and heteroaryl groups also include rings and ring systems in which a bond to a hydrogen atom may be replaced with a bond to a carbon atom. Substituted cycloalkyl, aryl, heterocyclyl and heteroaryl groups may also be substituted with substituted or unsubstituted alkyl, alkenyl, and alkynyl groups as defined below.

Alkyl groups include straight chain and branched chain alkyl groups having from 1 to 12 carbon atoms, and typically from 1 to 10 carbons or, in some examples, from 1 to 8, 1 to 6, or 1 to 4 carbon atoms. Examples of straight chain alkyl groups include groups such as methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, and n-octyl groups. Examples of branched alkyl groups include, but are not limited to, isopropyl, iso-butyl, sec-butyl, tert-butyl, neopentyl, isopentyl, and 2,2-dimethylpropyl groups. Representative substituted alkyl groups may be substituted one or more times with substituents such as those listed above and include, without limitation, haloalkyl (e.g., trifluoromethyl), hydroxyalkyl, thioalkyl, aminoalkyl, alkylaminoalkyl, dialkylaminoalkyl, alkoxyalkyl, or carboxyalkyl.

Cycloalkyl groups include mono-, bi- or tricyclic alkyl groups having from 3 to 12 carbon atoms in the ring(s), or, in some embodiments, 3 to 10, 3 to 8, or 3 to 4, 5, or 6 carbon atoms. Exemplary monocyclic cycloalkyl groups include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl groups. In some embodiments, the cycloalkyl group has 3 to 8 ring members, whereas in other embodiments, the number of ring carbon atoms ranges from 3 to 5, 3 to 6, or 3 to 7. Bi- and tricyclic ring systems include both bridged cycloalkyl groups and fused rings, such as, but not limited to, bicyclo[2.1.1]hexane, adamantyl, or decalinyl. Substituted cycloalkyl groups may be substituted one or more times with non-hydrogen and non-carbon groups as defined above. However, substituted cycloalkyl groups also include rings that may be substituted with straight or branched chain alkyl groups as defined above. Representative substituted cycloalkyl groups may be mono-substituted or substituted more than once, such as, but not limited to, 2,2-, 2,3-, 2,4-2,5- or 2,6-disubstituted cyclohexyl groups, which may be substituted with substituents such as those listed above.

Aryl groups may be cyclic aromatic hydrocarbons that do not contain heteroatoms. Aryl groups herein include monocyclic, bicyclic and tricyclic ring systems. Aryl groups include, but are not limited to, phenyl, azulenyl, heptalenyl, biphenyl, fluorenyl, phenanthrenyl, anthracenyl, indenyl, indanyl, pentalenyl, and naphthyl groups. In some embodiments, aryl groups contain 6-14 carbons, and in others from 6 to 12 or even 6-10 carbon atoms in the ring portions of the groups. In some embodiments, the aryl groups may be phenyl or naphthyl. Although the phrase “aryl groups” may include groups containing fused rings, such as fused aromatic-aliphatic ring systems (e.g., indanyl or tetrahydronaphthyl), “aryl groups” does not include aryl groups that have other groups, such as alkyl or halo groups, bonded to one of the ring members. Rather, groups such as tolyl may be referred to as substituted aryl groups. Representative substituted aryl groups may be mono-substituted or substituted more than once. For example, monosubstituted aryl groups include, but are not limited to, 2-, 3-, 4-, 5-, or 6-substituted phenyl or naphthyl, which may be substituted with substituents such as those above.

Aralkyl groups may be alkyl groups as defined above in which a hydrogen or carbon bond of an alkyl group may be replaced with a bond to an aryl group as defined above. In some embodiments, aralkyl groups contain 7 to 16 carbon atoms, 7 to 14 carbon atoms, or 7 to 10 carbon atoms. Substituted aralkyl groups may be substituted at the alkyl, the aryl or both the alkyl and aryl portions of the group. Representative aralkyl groups include but are not limited to benzyl and phenethyl groups and fused (cycloalkylaryl)alkyl groups such as 4-indanylethyl. Representative substituted aralkyl groups may be substituted one or more times with substituents such as those listed above.

Groups described herein having two or more points of attachment (i.e., divalent, trivalent, or polyvalent) within the compound of the technology may be designated by use of the suffix, “ene.” For example, divalent alkyl groups may be alkylene groups, divalent aryl groups may be arylene groups, divalent heteroaryl groups may be heteroarylene groups, and so forth. In particular, certain polymers may be described by use of the suffix “ene” in conjunction with a term describing the polymer repeat unit.

Alkoxy groups may be hydroxyl groups (—OH) in which the bond to the hydrogen atom may be replaced by a bond to a carbon atom of a substituted or unsubstituted alkyl group as defined above. Examples of linear alkoxy groups include, but are not limited to, methoxy, ethoxy, propoxy, butoxy, pentoxy, or hexoxy. Examples of branched alkoxy groups include, but are not limited to, isopropoxy, sec-butoxy, tert-butoxy, isopentoxy, or isohexoxy. Examples of cycloalkoxy groups include, but are not limited to, cyclopropyloxy, cyclobutyloxy, cyclopentyloxy, or cyclohexyloxy. Representative substituted alkoxy groups may be substituted one or more times with substituents such as those listed above.

The term “amine” (or “amino”), as used herein, refers to NR₅R₆ groups, wherein R₅ and R₆ may be independently hydrogen, or a substituted or unsubstituted alkyl, alkenyl, alkynyl, cycloalkyl, aryl, aralkyl, heterocyclylalkyl or heterocyclyl group as defined herein. In some embodiments, the amine may be alkylamino, dialkylamino, arylamino, or alkylarylamino. In other embodiments, the amine may be NH₂, methylamino, dimethylamino, ethylamino, diethylamino, propylamino, isopropylamino, phenylamino, or benzylamino The term “alkylamino” may be defined as NR₇R₈, wherein at least one of R₇ and R₈ may be alkyl and the other may be alkyl or hydrogen. The term “arylamino” may be defined as NR₉R₁₀, wherein at least one of R₉ and R₁₀ may be aryl and the other may be aryl or hydrogen.

The term “halogen” or “halo,” as used herein, refers to bromine, chlorine, fluorine, or iodine. In some embodiments, the halogen may be fluorine. In other embodiments, the halogen may be chlorine or bromine.

The various aspects and embodiments disclosed herein are for purposes of illustration and are not intended to be limiting, with the true scope and spirit being indicated by the following claims. 

1. A method for upgrading a bio-oil, the method comprising contacting the bio-oil with an olefin in the presence of a catalyst to form an upgraded bio-oil, the upgraded bio-oil comprising, compared to the bio-oil, one or more of: a reduced hydroxyl value; a reduced acid value; a reduced polarity; a reduced miscibility in a polar solvent; a reduced oxygen concentration, a reduced water concentration; or an increased average molecular weight.
 2. The method of claim 1, further comprising pyrolyzing a biomass to form the bio-oil prior to contacting the bio-oil with the olefin in the presence of the catalyst.
 3. The method of claim 1, the olefin comprising a C₃-C₅ alkene.
 4. The method of claim 1, the olefin comprising one or more of: propylene, isobutylene, or isoprene.
 5. The method of claim 1, further comprising contacting the bio-oil with a hydrogen donor.
 6. The method of claim 5, the hydrogen donor comprising a C₁-C₁₀ aliphatic compound that comprises at least one hydroxyl group bonded to an alkyl carbon.
 7. The method of claim 1, further comprising contacting the bio-oil with at least one of: a C₃-C₅ alcohol, a C₃-C₅ diol, or a C₃-C₅ triol.
 8. The method of claim 1, the catalyst comprising one or more of: a solid acid catalyst, a transition metal catalyst, a liquid phase acid catalyst, or a vapor phase acid catalyst.
 9. The method of claim 1, the catalyst comprising a supported propylsulfonic acid.
 10. The method of claim 1, the bio-oil being at least partially in a vapor phase.
 11. A method for upgrading bio-oil in a vapor phase, the method comprising: providing a vapor phase bio-oil; and contacting the vapor phase bio-oil with an olefin in the presence of a catalyst to provide an upgraded bio-oil.
 12. The method of claim 11, the upgraded bio-oil comprising, compared to the bio-oil, one or more of: a reduced hydroxyl value; a reduced acid value; a reduced polarity; a reduced miscibility in a polar solvent; a reduced oxygen concentration, a reduced water concentration; or an increased average molecular weight.
 13. The method of claim 11, further comprising: mixing the vapor phase bio-oil with the olefin in gas or vapor form to provide a vapor phase mixture of bio-oil and olefin; and contacting the vapor phase mixture of bio-oil and olefin to the catalyst to provide the upgraded bio-oil.
 14. The method of claim 11, conducted as a continuous process.
 15. The method of claim 11, the providing the vapor phase bio-oil comprising pyrolyzing a biomass to form the vapor phase bio-oil.
 16. The method of claim 11, the olefin comprising a C₃-C₅ alkene.
 17. The method of claim 11, the olefin comprising one or more of propylene, isobutylene, or isoprene.
 18. The method of claim 11, the catalyst comprising one or more of: a solid acid catalyst, a transition metal catalyst, a liquid phase acid catalyst, or a vapor phase acid catalyst.
 19. The method of claim 11, the catalyst comprising a supported propylsulfonic acid.
 20. The method of claim 11, the vapor phase bio-oil comprising water, further comprising separating an alcohol from the upgraded bio-oil, the alcohol produced by contacting the vapor phase bio-oil comprising water with the olefin in the presence of the catalyst.
 21. A process for converting a pyrolysis oil to one or more hydrocarbon fuel range products, the process comprising: (a) reacting a pyrolysis oil with a feed comprising an olefin in the presence of a catalyst to form a product mixture comprising at least one of an esterification product and an etherification product; and (b) contacting the at least one of the esterification product and the etherification product in a reaction zone with a hydrotreating catalyst in the presence of hydrogen under reaction conditions sufficient to convert at least a portion of the at least one of the esterification product and the etherification product into one or more fuel range hydrocarbon products.
 22. The process of claim 21, further comprising pyrolyzing a biomass to form the pyrolysis oil prior to reacting the pyrolysis oil with the feed comprising the olefin in the presence of the catalyst.
 23. The process of claim 21, wherein the olefin comprises a C₃-C₅ alkene.
 24. The process of claim 21, the olefin comprising one or more of propylene, isobutylene, or isoprene.
 25. The process of claim 21, further comprising contacting the pyrolysis oil with a hydrogen donor.
 26. The process of claim 25, the hydrogen donor comprising one or more of: a C₁-C₁₀ aliphatic compound that comprises at least one hydroxyl group bonded to an alkyl carbon.
 27. The process of claim 21, further comprising contacting the pyrolysis oil with at least one of: a C₃-C₅ alcohol, a C₃-C₅ diol, or a C₃-C₅ triol.
 28. The process of claim 21, the catalyst comprising one or more of: a solid acid catalyst, a transition metal catalyst, a liquid phase acid catalyst, or a vapor phase acid catalyst.
 29. The process of claim 21, wherein the catalyst comprises a supported propylsulfonic acid.
 30. The process of claim 21, wherein the pyrolysis oil is at least partially in a vapor phase.
 31. The process of claim 21, wherein the hydrotreating catalyst comprises one or more catalysts selected from the group consisting of: cobalt (Co), molybdenum (Mo), nickel (Ni), titanium (Ti), tungsten (W), zinc (Zn), antimony (Sb), bismuth (Bi), cerium (Ce), vanadium (V), niobium (Nb), tantalum (Ta), chromium (Cr), manganese (Mn), rhenium (Re), iron (Fe), platinum (Pt), iridium (Ir), palladium (Pd), osmium (Os), rhodium (Rh), ruthenium (Ru), nickel, copper impregnated zinc oxide (Cu/ZnO), copper impregnated chromium oxide (Cu/Cr), nickel aluminum oxide (Ni/Al₂O₃), palladium aluminum oxide (PdAl₂O₃), cobalt molybdenum (CoMo), nickel molybdenum (NiMo), nickel molybdenum tungsten (NiMoW), sulfided cobalt molybdenum (CoMo), sulfided nickel molybdenum (NiMo), and a metal carbide; or a composite or combination thereof.
 32. The process of claim 21, wherein the hydrotreating catalyst comprises: a) a metal oxide support selected from the group consisting of a titanium oxide (TiO₂) support, a silicon oxide support, a zirconia oxide (ZrO₂) support, a niobium oxide (Nb₂O₅) support, and a support comprising one or more mixtures of non-alumina metal oxides; and b) a noble metal composition on the metal oxide support, the noble metal composition comprising one or more noble metals selected from the group consisting of: rhodium (Rh), palladium (Pd), gold (Au), and ruthenium (Ru).
 33. An upgraded bio-oil, the upgraded bio-oil produced by a process comprising contacting a crude bio-oil with an olefin in the presence of a catalyst to form the upgraded bio-oil, the upgraded bio-oil comprising, compared to the crude bio-oil, one or more of: a reduced hydroxyl value; a reduced acid value; a reduced polarity; a reduced miscibility in a polar solvent; a reduced oxygen concentration, a reduced water concentration; or an increased average molecular weight.
 34. An upgraded bio-oil, the upgraded bio-oil produced by a process comprising: providing a vapor phase bio-oil; and contacting the vapor phase bio-oil with an olefin in the presence of a catalyst to provide the upgraded bio-oil.
 35. A composition comprising one or more hydrocarbon fuel range products, the mixture of one or more hydrocarbon fuel range products produced from a pyrolysis oil by a process comprising: (a) reacting the pyrolysis oil with a feed comprising an olefin in the presence of a catalyst to form a product mixture comprising at least one of an esterification product and an etherification product; and (b) contacting the at least one of the esterification product and the etherification product in a reaction zone with a hydrotreating catalyst in the presence of hydrogen under reaction conditions sufficient to convert at least a portion of the at least one of the esterification product and the etherification product into the mixture of the one or more fuel range hydrocarbon products.
 36. A method 800 of improving miscibility of a bio-oil in a hydrophobic fuel, comprising: 802 providing a miscible bio-oil, the miscible bio-oil being upgraded, catalytic, or upgraded and catalytic compared to a starting material bio-oil; and 804 contacting the miscible bio-oil to a hydrophobic fuel to form a miscible mixture, the miscible bio-oil being characterized by greater miscibility in the hydrophobic fuel compared to the bio-oil starting material.
 37. The method of claim 36, further comprising contacting an alcohol to the miscible bio-oil and the hydrophobic fuel to form the miscible mixture.
 38. The method of claim 37, the alcohol including a C₃-C₅ alcohol.
 39. The method of claim 37, the alcohol including one or more of n-butanol, sec-butanol, iso-butanol, tert-butanol, n-propanol, or 2-propanol.
 40. The method of claim 36, further comprising contacting a surfactant to the miscible bio-oil and the hydrophobic fuel to form the miscible mixture.
 41. The method of claim 40, the surfactant including one or more of an anionic surfactant, a cationic surfactant, an amphiphilic surfactant, or a nonionic surfactant.
 42. The method of claim 36, further comprising contacting a surfactant and an alcohol to the miscible bio-oil and the hydrophobic fuel to form the miscible mixture.
 43. The method of claim 36, including upgrading the bio-oil starting material to provide the miscible bio-oil by one or more of: contacting the bio-oil starting material with an olefin in the presence of a solid acid catalyst to provide the miscible bio-oil; or contacting the bio-oil starting material with the olefin in a vapor phase in the presence of a catalyst to provide the miscible bio-oil, the miscible bio-oil being reduced in one or more of a hydroxyl value, an acid value, or a water concentration compared to the bio-oil starting material.
 44. The method of claim 36, the hydrophobic fuel including one or more of: diesel, fuel oil, heating oil, bunker fuel, gasoline, jet fuel, kerosene, white gas, liquefied coal fuel, or naphtha.
 45. The method of claim 36, the bio-oil starting material including one or more of: water, organic acids, aldehydes, alkyl hydroxyls, phenols, or sugars.
 46. A bio-oil composition, comprising a miscible ternary mixture according to each triplet of miscible or partly miscible ranges in any one of FIG. 7A, 7B, 7C, or 7D, or a combination thereof, including: a bio-oil, an upgraded bio-oil, a catalytic bio-oil, or an upgraded catalytic bio-oil in a percentage according to each corresponding range; an alcohol in a percentage according to each corresponding range of 1-butanol; and a hydrophobic fuel in a percentage according to each corresponding range of diesel.
 47. The bio-oil composition of claim 46, the miscible ternary mixture being according to each triplet of miscible or partly miscible ranges in any one of FIG. 7B, 7C, or 7D, or a combination thereof.
 48. The bio-oil composition of claim 46, at least one said percentage being within the corresponding miscible percentage range.
 49. The bio-oil composition of claim 46, each said corresponding percentage range being within each corresponding miscible percentage range.
 50. The bio-oil composition of claim 46, consisting substantially of the miscible ternary mixture.
 51. The bio-oil composition of claim 46, consisting essentially of the miscible ternary mixture.
 52. The bio-oil composition of claim 46, the alcohol including a C₃-C₅ alcohol.
 53. The bio-oil composition of claim 46, the alcohol including one or more of n-butanol, sec-butanol, iso-butanol, tert-butanol, n-propanol, or 2-propanol.
 54. The bio-oil composition of claim 46, the hydrophobic fuel including one or more of: diesel, fuel oil, heating oil, bunker fuel, gasoline, jet fuel, kerosene, white gas, liquefied coal fuel, or naphtha.
 55. The bio-oil composition of claim 46, further comprising a surfactant.
 56. The bio-oil composition of claim 46, further comprising one or more of an anionic surfactant, a cationic surfactant, an amphiphilic surfactant, or a nonionic surfactant.
 57. The bio-oil composition of claim 46, the miscible bio-oil being prepared from a bio-oil starting material in a process including one or more of: contacting the bio-oil starting material with an olefin in the presence of a solid acid catalyst to provide the miscible bio-oil; or contacting the bio-oil starting material with the olefin in a vapor phase in the presence of a catalyst to provide the miscible bio-oil, the miscible bio-oil being reduced in one or more of a hydroxyl value, an acid value, and a water concentration compared to the bio-oil starting material. 